JP6499200B2 - Crosslinking catalyst having polyether structural unit - Google Patents

Description

  The present invention relates to a catalyst for a curable composition, especially for a silane group-containing composition.

  Curable compositions play an important role in many technical applications, for example as adhesives, sealants or coatings. The curing takes place by a crosslinking reaction that proceeds via free or latent reactive groups such as isocyanate groups, epoxide groups, hydroxyl groups, amino groups, or silane groups, which are then mixed after the mixing process. Reacts with itself or with each other by heating or contact with moisture, and thus the constituents contained in the composition are covalently bonded into a polymer network. In order to promote such a crosslinking reaction, a catalyst is often used. It is a toxicologically alarming substance that can be harmful to the processor and the environment, especially when the catalyst or its degradation products are released by outgassing, migration, or leaching, after curing of the composition There are many cases.

  Clearly, room temperature curable compositions based on silane group-containing polymers face this problem. Silane group-containing polymers are, in particular, polyorganosiloxanes commonly referred to as “silicones” or “silicone rubbers” and “silane-functional polymers”, “silane-modified polymers” (SMP) or “silane-terminated polymers”, among others. It is a silane group-containing organic polymer also called (STP). Their crosslinking proceeds while forming siloxane bonds by condensation of silanol groups and is conventionally catalyzed by organotin compounds such as, inter alia, dialkyltin (IV) carboxylates. They are characterized by very good activity with respect to silanol condensation and have very high resistance to hydrolysis; however, they are harmful to health and water pollution. They are often combined with other catalysts, mainly basic compounds that promote hydrolysis of the upstream silane groups, for example, especially amines.

  The importance of EHS aspects by trade associations and consumers has increased, and national regulations have become more stringent, and efforts have been made to use other relatively less toxic catalysts instead of organotin compounds for some time. Yes. For example, organic titanates, organic zirconates, and organic aluminates have been described as alternative metal catalysts. However, in most cases they are relatively low in catalytic activity with respect to silanol condensation and crosslinking is much slower. Because of their lack of hydrolytic stability, they can lose most of their activity due to residual moisture in the components upon storage of the composition, which can result in a very slow or slow cure. Stop completely.

  Other known alternatives of organotin compounds are the strongly basic nitrogen compounds of amidines and guanidines that can be used in combination with the aforementioned metal catalysts or alone. Many of the common amidine and guanidine catalysts such as, among others, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 1,1,3,3-tetramethylguanidine (TMG) However, it is easily volatile and has a strong odor, as well as a health hazard and an environmental hazard. Moreover, they tend to migrate due to poor compatibility in the composition, thereby causing separation, bleed or substrate contamination. Countermeasures are taken with the use of aromatic amidines and guanidines which are solid at room temperature as described above, but this requires the use of a suitable solvent, which impairs the catalytic activity and thus the crosslinking rate.

  The object of the present invention is therefore to have a high catalytic activity for the crosslinking reaction, thus enabling rapid curing of the applied composition and a high selectivity for this crosslinking reaction, Therefore, it is to provide a catalyst for crosslinking a curable composition, especially a silane group-containing composition, which does not unduly impair the storage stability of the composition. In addition, the catalyst must have low vapor pressure and high compatibility with the composition, be as odorless and as toxic as possible, so that the catalyst does not tend to separate or migrate or evaporate. It must be liquid at room temperature so that the catalyst can be used without solvent.

  These problems are solved by the catalyst of claim 1. The catalyst of claim 1 contains an aliphatic amidine group or guanidine group and exhibits high catalytic activity, but aromatic amidine or guanidine has little or no catalytic activity. In contrast to many of the aliphatic amidine or guanidine catalysts known from the prior art, it is odorless, liquid at room temperature and surprisingly low viscosity. It exhibits very high catalytic activity with good selectivity, especially in silane group-containing compositions. This is particularly surprising because of the relatively high molecular weight, which is expected to be low and therefore low compared to mobile amidines or guanidines.

  Due to these properties, the catalyst of claim 1 is very suitable for use in a silane group-containing composition, which can be used as a single catalyst or in other ways without compromising the shelf life of the uncured composition. In combination with a catalyst, it allows for rapid curing to highly mechanically resistant materials. Surprisingly, it is highly compatible with the curable composition before and after curing and does not tend to separate or migrate. In that case, the catalyst does not contain a functional group such as, for example, a silane group that can allow incorporation into the cured polymer, but when the catalyst is used as a cross-linking catalyst in a curable composition, during its curing. It is particularly surprising that it does not migrate to the surface. While the catalyst typically does not bind to the polymer when cured, it allows for a product with low release and odor that is free of surface stickiness, tackiness, and does not cause substrate contamination. Finally, the catalyst of claim 1 can be produced in a surprisingly simple and rapid manner from commercially available inexpensive starting materials without aids.

  Other aspects of the invention are the subject of other independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims.

｛式中、
ｎは１または２または３を表し、
Ａはポリオキシアルキレン基またはポリオキシアルキル化化合物の基を表し、場合により１個または２個の末端第１級または第２級アミノ基またはヒドロキシル基を有し、
Ｚは、式

または

（式中、
Ｒ^１およびＲ^０は、互いに独立してそれぞれ、水素、または炭素数１〜８のアルキル基もしくはシクロアルキル基もしくはアラルキル基を表し、
Ｒ^２は、水素、または場合によりヘテロ原子を含有し、場合により末端第１級もしくは第２級アミノ基を有する炭素数１〜１８のアルキル基、シクロアルキル基、もしくはアラルキル基を表し、
Ｒ^３は、−ＮＲ^４Ｒ^５、または水素、または炭素数１〜１２のアルキル基、シクロアルキル基、もしくはアラルキル基を表し、
Ｒ^４およびＲ^５は、互いに独立してそれぞれ、水素、または場合によりヘテロ原子を含有する炭素数１〜１８のアルキル基、シクロアルキル基、もしくはアラルキル基を表し、
Ｒ^１とＲ^２はまた一緒になって、炭素数２〜６のアルキレン基を表してもよく、
Ｒ^２とＲ^０はまた一緒になって、場合によりヘテロ原子を含有する炭素数３〜６のアルキレン基を表してもよく、
Ｒ^２とＲ^３はまた一緒になって、炭素数３〜６のアルキレン基を表してもよく、
Ｒ^４とＲ^５はまた一緒になって、場合によりヘテロ原子を含有する炭素数４〜７のアルキレン基を表してもよく、
Ｒ^２とＲ^５はまた一緒になって、炭素数２〜１２のアルキレン基を表してもよい）
の基を表す｝
の触媒であり、
式（Ｉ）の触媒は、芳香環、または例えばイミダゾールもしくはピリミジンのような芳香族複素環系の一部に直接結合している窒素原子を含有しない。 The subject of the present invention is a compound of formula (I)

{Where
n represents 1 or 2 or 3;
A represents a polyoxyalkylene group or a group of a polyoxyalkylated compound, optionally having one or two terminal primary or secondary amino groups or hydroxyl groups;
Z is the formula

Or

(Where
R ¹ and R ⁰ each independently represent hydrogen, or an alkyl group, cycloalkyl group, or aralkyl group having 1 to 8 carbon atoms,
R ² represents hydrogen or an optionally substituted hetero atom, optionally a terminal primary or secondary amino group having 1 to 18 carbon atoms, a cycloalkyl group, or an aralkyl group,
R ³ represents —NR ⁴ R ⁵ , hydrogen, or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or an aralkyl group,
R ⁴ and R ⁵ each independently represent hydrogen or an optionally substituted alkyl group, cycloalkyl group, or aralkyl group containing 1 to 18 carbon atoms,
R ¹ and R ² together may represent an alkylene group having 2 to 6 carbon atoms,
R ² and R ⁰ together may optionally represent a C 3-6 alkylene group containing a heteroatom,
R ² and R ³ together may represent a C 3-6 alkylene group,
R ⁴ and R ⁵ together may also represent a C 4-7 alkylene group optionally containing a heteroatom,
R ² and R ⁵ together may represent an alkylene group having 2 to 12 carbon atoms)
Represents the base of
The catalyst of
The catalyst of formula (I) does not contain a nitrogen atom which is directly bonded to an aromatic ring or part of an aromatic heterocyclic system such as imidazole or pyrimidine.

  In this document, the term “silane group” refers to a silyl group bonded to an organic group or to a polyorganosiloxane group having 1 to 3, especially 2 or 3, hydrolyzable substituents on a silicon atom. Point to. In that case, the hydrolyzable substituent is in particular an alkoxy group having 1 to 13 carbon atoms, an acetoxy group, a ketoxymato group, an amide group or an enoxy group, preferably an alkoxy group or a ketoximato group, particularly preferably an alkoxy group. Yes; the latter silane group is referred to below as the “alkoxysilane group”. The term “silane group” is further understood by definition as a silanol group corresponding to a partially or fully hydrolyzed silane group and having one or more hydroxyl groups on the silicon atom.

  “Hydroxysilane”, “isocyanatosilane”, “aminosilane” or “mercaptosilane” means one or more hydroxyl groups, isocyanato groups, amino groups or mercapto groups in addition to silane groups on an organic group. The organoalkoxysilane which has.

  Substance names beginning with “poly”, such as polyols or polyisocyanates, by definition refer to substances containing two or more functional groups from which the name is derived per molecule.

  The term “organic polymer” is produced by a polymerization reaction (polymerization, polyaddition, polycondensation) and has mainly carbon atoms in the polymer backbone, which is chemically uniform but with a degree of polymerization, molar mass and chain length. And a group of macromolecules distinguished with respect to, as well as reaction products of such macromolecule populations. A polymer having a polydiorganosiloxane skeleton (commonly referred to as “silicone”) is not an organic polymer in the sense of this document.

  The term “silane group-containing polyether” also encompasses silane group-containing organic polymers that can also contain urethane groups, urea groups, or thiourethane groups in addition to the polyether units. Such a silane group-containing polyether can also be referred to as a “silane group-containing polyurethane”.

“Molecular weight” is understood in this document as the molar mass (grams per mole) of a molecule, or part of a molecule, also referred to as a “group”. “Average molecular weight” refers to the number average M _n of an oligomer or polymer mixture of molecules or groups, usually determined by polystyrene permeation chromatography (GPC) relative to polystyrene as a standard.

  The substance or composition can be stored in a suitable container at room temperature for a relatively long time, typically without changes in storage, to the extent relevant to its use, its application or use characteristics, especially viscosity and crosslinking rate. When it can be stored for at least 3 months to 6 months or more, it is called “storage stability” or “storability”.

  Each broken line in the formula of this document indicates a bond between a substituent and an attached molecular group.

  “Room temperature” refers to a temperature of about 23 ° C.

  The catalyst of formula (I) may also exist in tautomeric form. All possible tautomers of the catalyst of formula (I) are considered equivalent for the purposes of the present invention.

  Furthermore, the catalyst of formula (I) may exist in protonated form.

  Similarly, the catalyst of formula (I) may be present in a complexed form, especially in a complexed form with zinc, iron or molybdenum cations.

  In the catalyst of formula (I), the average molecular weight of A is preferably in the range of 180 to 5,000 g / mol, particularly preferably 200 to 2,000 g / mol. These catalysts of formula (I) are particularly easily obtainable and have a low viscosity.

  Polyoxyalkylene groups suitable as A are inter alia oxiranes, in particular ethylene oxide and / or 1,2-propylene oxide and / or 1,2-butylene oxide, starting material molecules having two active hydrogen atoms, in particular Water, glycols such as 1,2-ethanediol, 1,2- or 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2- or 1,3- or 1,4- Butanediol, 1,3- or 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2- or 2,5- or 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol Ethylene glycol, polyethylene glycol, dipropylene glycol, tri B is propylene glycol, polypropylene glycol or poly polyoxyalkylene groups obtained by polyaddition (tetramethylene ether) glycol.

  Other polyoxyalkylene groups suitable as A are optionally poly (5) obtained by ring-opening polymerization of tetrahydrofuran with a part of another oxyalkylene unit such as, among others, a 1,2-oxypropylene unit or an oxybutylene unit. Oxytetramethylene) group.

Groups of polyoxyalkylated compounds suitable as A have oxiranes such as ethylene oxide and / or 1,2-propylene oxide and / or 1,2-butylene oxide, especially having 1 to 3 active hydrogen atoms. Cresol to starting material molecules, especially alcohols such as fatty alcohol mixtures derived from natural fats such as methanol, ethanol, isopropanol, butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, or _C12-14 fatty alcohols 1,4-dimethylolcyclohexane or 3 (4), 8 (9) -bis (hydroxymethyl), phenols such as tert-butylphenol, nonylphenol or dodecylphenol or alkylphenols ) To diols such as tricyclo [5.2.1.0 ^2,6 ] decane, to diphenols such as bisphenol F or bisphenol A, or to triols such as glycerin or 1,1,1-trimethylolpropane. This is a group obtained by polyaddition.

  Particularly preferably, A is optionally a polyoxypropylene group having a part of another oxyalkylene unit such as, in particular, an oxyethylene unit or a 1,2-oxybutylene unit, or optionally a 1,2-oxypropylene unit. A poly (oxytetramethylene) group having a moiety, or polyoxyalkyl obtained by polyaddition of 1,2-propylene oxide to a starting material molecule selected from the group consisting of alcohols, fatty alcohols, alkylphenols, diols, and triols Represents a 1-3 valent group of the compound. These catalysts of formula (I) can be obtained particularly easily and are particularly excellent in compatibility with the curable composition.

  Most preferably, A represents a polyoxypropylene group having an average molecular weight in the range of 200 to 2,000 g / mol.

  Preferably A is substantially free of primary or secondary amino groups and / or hydroxyl groups.

  n preferably represents 1 or 2, especially 2.

R ¹ and R ⁰ preferably each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, especially hydrogen.

R ² preferably represents hydrogen or an alkyl group, cycloalkyl group or aralkyl group having 1 to 12 carbon atoms, especially 1 to 8 carbon atoms, optionally containing a hetero atom.

R ³ preferably represents —NR ⁴ R ⁵ , hydrogen, or an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, or an aralkyl group.

Particularly preferably R ³ represents —NR ⁴ R ⁵ .

R ⁴ and R ⁵ preferably each independently represent hydrogen, or an alkyl group, cycloalkyl group or aralkyl group having 1 to 12 carbon atoms which optionally contains an oxygen atom or a nitrogen atom.

More preferably, R ⁴ and R ⁵ together represent a C 4-7 alkylene group optionally containing an oxygen atom or a nitrogen atom.

More preferably, R ¹ and R ² together represent an alkylene group having 2 to 4 carbon atoms, especially 2 or 3 carbon atoms.

More preferably, R ² and R ⁰ together represent a C 4-6 alkylene group optionally containing a heteroatom.

More preferably, R ² and R ³ together represent an alkylene group having 3 to 5 carbon atoms.

More preferably, R ² and R ⁵ together represent an alkylene group having 2 to 4 carbon atoms.

Particularly preferably R ⁴ represents hydrogen.

  Preferred embodiments of the catalyst of formula (I) can be prepared from commercially available inexpensive raw materials and have particularly good properties with respect to catalytic activity and compatibility in curable compositions, especially silane group-containing compositions. Have

In one embodiment of the invention, in the catalyst of formula (I), R ³ represents hydrogen or an alkyl, cycloalkyl or aralkyl group having 1 to 12, preferably 1 to 8, especially 1 to 4 carbon atoms. R ² and R ³ together represent an alkylene group having 3 to 6 carbon atoms, especially 3 to 5 carbon atoms.

  These catalysts of formula (I) have an amidine group.

Preferably R ³ represents hydrogen or methyl, especially methyl.

Preferably R ¹ represents hydrogen or together with R ² represents 1,2-ethylene or 1,3-propylene.

Preferably R ² represents hexyl, cyclohexyl, benzyl, 2-ethylhexyl, octyl, decyl, dodecyl or 2-methoxyethyl, or together with R ¹ , 1,2-ethylene or 1,3-propylene Represents.

  Preferred embodiments of the catalyst of formula (I) having amidine groups are characterized by good catalytic activity and excellent compatibility in the curable composition.

  Compared to the catalysts of the formula (I) with guanidine groups, they are not very catalytically active and can therefore be used in somewhat larger quantities, so that they are the other components of the composition, In particular, there is an advantage that problems due to impurities contained therein hardly occur.

In a preferred embodiment of the invention, in the catalyst of formula (I), R ³ represents —NR ⁴ R ⁵ .

  These catalysts of formula (I) have a guanidine group. They are characterized by low viscosity, higher catalytic activity compared to catalysts having amidine groups, and excellent compatibility in curable compositions.

In the catalyst of formula (I) having a guanidine group,
R ⁴ preferably represents hydrogen,
R ² and R ⁵ preferably each independently represent a C 1-18 alkyl group, cycloalkyl group or aralkyl group optionally containing a heteroatom,
R ¹ preferably represents hydrogen.

を有する。 Preferred embodiments of the catalyst of formula (I) having a guanidine group are represented by formula (Ia)

Have

  The catalyst of formula (Ia) can be prepared particularly easily and has a particularly high catalytic activity.

R ² and R ⁵ particularly preferably each independently represent ethyl, isopropyl, tert-butyl, 3- (dimethylamino) propyl or cyclohexyl, in particular each represent isopropyl or cyclohexyl, most preferably each cyclohexyl. Represent.

  These catalysts can be obtained particularly easily.

  Particularly preferred catalysts of the formula (I) having guanidine groups are 1,1 ′-(α, ω-polyoxypropylene) bis (2,3-diisopropylguanidine) having a molecular weight in the range of about 470 to 2,300 g / mol. And 1,1 ′-(α, ω-polyoxypropylene) bis (2,3-dicyclohexylguanidine) having a molecular weight in the range of about 630 to 2,500 g / mol.

  The catalyst of formula (I) comprises, inter alia, at least one polyetheramine, orthoester, 1,3-ketoester, 1,3-ketoamide, nitrile, imidoester, imidoacid chloride, amide, lactam, cyanamide. At least one for introducing an amidine group or a guanidine group selected from the group consisting of carbodiimide, urea, O-alkylisourea, thiourea, S-alkylisothiourea, aminoiminomethanesulfonic acid, guanylpyrazole and guanidine It can be obtained by reacting with the above reagents.

  Orthoesters, 1,3-ketoesters, 1,3-ketoamides, nitriles, imidoesters, imidoacid chlorides, amides and lactams, especially orthoesters, 1,3-ketoesters and nitrites are suitable for the introduction of amidine groups ing.

In a preferred process for preparing the catalyst of formula (I), wherein R ³ represents hydrogen or an alkyl, cycloalkyl or aralkyl group having 1 to 12 carbon atoms, at least one polyetheramine is substituted with at least one orthoamine. Reaction with an ester, or at least one 1,3-keto ester, or at least one nitrile. At that time, a catalyst of formula (I) having an amidine group is formed.

  Preferred orthoesters are orthoformate, orthoacetate, orthopropionate, orthobutyrate and orthovalerate, especially trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate and triethyl orthoacetate.

  Preferred 1,3-ketoesters are methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, or tert-butyl acetoacetate, especially ethyl acetoacetate.

  Preferred nitriles are acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile and capronitrile, especially acetonitrile.

Preferably, the catalyst of formula (I) having an amidine group comprises at least one polyetheramine, at least one orthoester of formula R ³ —C (OR ^a ) ₃ and optionally of formula R ² —NH—. It is obtained by reacting with at least one monoamine of R ⁰ , particularly R ² —NH _2, and removing the alcohol R ^a OH (wherein R ^a represents an alkyl group having 1 to 4 carbon atoms in particular). . This reaction is preferably carried out in the presence of a catalyst at elevated temperatures, in particular at 40 to 160 ° C., particularly preferably at 60 to 140 ° C. and at elevated pressure.

More preferably, the catalyst of formula (I) having an amidine group comprises at least one polyetheramine and at least one 1,3- of formula R ³ —C (O) CH ₂ C (O) OR ^a. Obtained by reaction with ketoester. This reaction is preferably carried out at a temperature of 20 to 100 ° C., in particular 40 to 80 ° C., at which time the eliminated ester CH ₃ C (O) OR ^a is preferably distilled off. Preferably, in that case, a catalyst, in particular an acid, preferably a sulfonic acid, is used.

  Preferred monoamines for this purpose are n-hexylamine, cyclohexylamine, benzylamine, 2-ethylhexylamine, n-octylamine, n-decylamine, laurylamine and 2-methoxyethylamine.

  The reaction can be carried out in one step or in multiple steps.

  The reaction product of this process is preferably used in the composition without any work-up and / or purification, except that the volatile compounds are optionally distilled off under reduced pressure.

  The use of polyether diamines or polyether triamines typically produces a mixture containing an oligomer byproduct having a plurality of amidine groups in addition to the desired catalyst of formula (I).

  In that case, in order to keep the by-product formation low, the reaction is preferably such that at least 2 mol of polyether diamine or 3 mol of polyether triamine are used per mol of orthoester or 1,3-ketoester. Done. The resulting catalyst of formula (I) has a primary or secondary amino group.

  In addition to polyether diamine or polyether triamine, the use of additional monoamines also results in relatively low oligomer by-products. In this case, the reaction is preferably at least 2 mol of the monoamine of the above formula per mol of polyether diamine, or at least 3 mol of the monoamine of the formula and at least 1 mol of orthoester or mol of 1 mol of polyether triamine. The ketoester is used. The resulting catalyst of formula (I) does not contain a primary or secondary amino group.

When using aminopropylated polyetheramine, the reaction is preferably carried out such that about 1 mol of orthoester or 1,3-ketoester is used for each aminopropylamino group. A catalyst of formula (I) having at least one amidine group is then obtained, in which R ¹ and R ² together represent 1,3-propylene. The following formula illustrates the reaction product obtained from a 2/1 molar ratio of orthoacetic acid ester and double aminopropylated polyoxypropylene diamine:

  When the catalyst of formula (I) has a cyclic amidine group, a 6-membered ring is preferred because of its high catalytic activity.

  For the introduction of guanidine groups, cyanamide, carbodiimide, urea, O-alkylisourea, thiourea, S-alkylisothiourea, aminoiminomethanesulfonic acid, guanylpyrazole and guanidine are suitable. Preference is given to cyanamide and carbodiimide.

  Particularly preferred is carbodiimide. In this way, a particularly highly active catalyst of formula (I) is obtained in a particularly simple manner.

In another preferred method of preparing the catalyst of formula (I), wherein R ³ represents —NR ⁴ R ⁵ , at least one polyetheramine of formula A- (NHR ¹ ) _n is represented by formula R ⁵ -N = C = are reacted with at least one carbodiimide ^{N-R 2.} A catalyst of the formula (Ia) containing in particular a guanidine group is then produced. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n have the aforementioned meanings.

  As carbodiimides, typically aliphatic, cycloaliphatic or arylaliphatic carbodiimides, especially simple commercial aliphatic and cycloaliphatic carbodiimides, preferably N, N′-diisopropylcarbodiimide (DIC), N, N ′. -Di-tert-butylcarbodiimide, N, N'-dicyclohexylcarbodiimide (DCC) or N-ethyl-N '-(3-dimethylaminopropyl) carbodiimide (EDC), particularly preferably N, N'-diisopropylcarbodiimide ( DIC) or N, N′-dicyclohexylcarbodiimide (DCC), especially DCC.

  The reaction between the polyetheramine and the carbodiimide is preferably carried out at an elevated temperature, in particular at 40 to 160 ° C., particularly preferably at 60 to 140 ° C. The reaction can be carried out without using any VOC solvent. To promote the reaction, a catalyst, especially an acid such as carboxylic acid or carbonic acid, or, for example, boron trifluoride etherate, aluminum chloride, aluminum acetylacetonate, iron (III) chloride, lithium perchlorate Lewis acids such as zinc chloride, zinc acetate, zinc neodecanoate, zinc acetylacetonate, zinc triflate, or lanthanum triflate can be used.

  The reaction can be carried out in one step or in multiple steps.

  In the reaction, carbodiimide is preferably used in such an amount that 1 mol or less of carbodiimide is present per equivalent of guanidine group formed.

  In particular, carbodiimide is used stoichiometrically with respect to the amino group of the polyetheramine. In this way, the resulting catalyst of formula (I) is substantially free of primary or secondary amino groups.

  The reaction product of this process is preferably used without workup and / or purification, except that the volatile compounds are optionally distilled off under reduced pressure.

Suitable polyether amines for preparing the catalyst of formula (I) are, for example, Jeffamine® (manufactured by Huntsman), polyether amine (manufactured by BASF), or PC Amine® (Nitroil). Polyoxyalkylene or polyoxyalkylated compounds having a terminal amino group, such as those commercially available under the trade name of the product, especially those having an average molecular weight in the range of about 200 to 5,000 g / mol, in particular Is:
Polyetherdiamines having 2-aminopropyl end groups or 2-aminobutyl end groups, in particular Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine ( (Registered trademark) D-4000, Jeffamine (registered trademark) XTJ-582, Jeffamine (registered trademark) XTJ-578, Jeffamine (registered trademark) HK-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED- 900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) XTJ-568, Jeffamine (registered trademark) XTJ-569, Jeffamine (registered trademark) THF-1 0, Jeffamine (TM) THF-140, Jeffamine (all manufactured by Huntsman) (R) THF-230, Jeffamine (R) XTJ-533 or Jeffamine (R) XTJ-536.
Polyether diamines having 4-aminobutyl end groups obtained by amination of poly (tetramethylene ether) glycol, in particular Jeffamine® THF-170 (manufactured by Huntsman).
-Polyether monoamines, especially those of the type starting from alcohol, for example Jeffamine® M-600, Jeffamine® M-1000, Jeffamine® M-2005, Jeffamine® M- 2070, Jeffamine (R) XTJ-581, Jeffamine (R) XTJ-249, Jeffamine (R) XTJ-435, or types starting from alkylphenols, such as Jeffamine (R) XTJ-436 (all Huntsman).
Polyether diamines obtained by polyalkoxylation of diols, in particular propoxylated 1,4-dimethylolcyclohexane, for example Jeffamine® RFD-270 (manufactured by Huntsman).
-Polyethertriamines, especially Jeffamine (R) T-403, Jeffamine (R) T-3000, Jeffamine (R) T-5000 or Jeffamine (R) XTJ-566 (all from Huntsman).
-Polyetheramines having secondary amino groups, especially Jeffamine® SD-231, Jeffamine® SD-401, Jeffamine® SD-2001, or Jeffamine® ST-404 ( All manufactured by Huntsman).
An aminopropylated polyetheramine, such as obtained by reacting a polyetheramine with acrylonitrile followed by hydrogenation.

  Of these, polyetheramines having primary amino groups are preferred.

  Of these, polyetheramines having an average molecular weight in the range of about 220 to 2,000 g / mol are further preferred.

  Preferred polyetheramines optionally have a polyoxypropylene diamine having a part of another oxyalkylene unit, such as an oxyethylene unit or a 1,2-oxybutylene unit, or optionally 1,2-oxypropylene unit. 1,2-oxypropylene obtained by polyaddition of poly (tetramethylene ether) diamine or 1,2-propylene oxide to a starting material molecule selected from the group consisting of alcohol, fatty alcohol, alkylphenol, diol, and triol It is a polyether monoamine or polyether diamine or polyether triamine having mainly units.

  Particularly preferably, the polyetheramine is a polyoxypropylene diamine having an average molecular weight in the range of about 220 to 2,000 g / mol.

  Most preferably, the polyetheramine is a polyoxypropylene diamine having an average molecular weight in the range of about 400-500 g / mol, especially Jeffamine® D-400 or Jeffamine® XTJ-582 (both from Huntsman) or PC-Amine (registered trademark) DA400 (manufactured by Nitroil) or polyetheramine D400 (manufactured by BASF).

  In a preferred embodiment of the process for preparing the catalyst of formula (I), it is prepared in the presence of a silane group-containing polymer. For this purpose, the polyetheramine and the reagent for introducing amidine groups or guanidine groups into the silane group-containing polymer are dissolved or suspended and reacted at an elevated temperature, in particular in the range from 40 to 120 ° C. In the production of such a catalyst of the formula (I), a catalyst is finally formed after a certain amount of time, which is particularly advantageous since it can be practically advantageous.

  This production method is particularly advantageous for the reaction of polyetheramines with carbodiimides.

  The catalyst of formula (I) can be used inter alia to promote crosslinking of the curable composition. Examples of suitable curable compositions include epoxy resin compositions, especially thermosets that crosslink with dicyandiamide or carboxylic acids or carboxylic anhydrides, such as those used in adhesives, coating materials and casting resins, for example. System; a polyurethane composition, in particular a two-component system that crosslinks by reaction of polyol and isocyanate, such as used in adhesives, coatings, castings, seal joints, molded bodies, or slab foams, for example. And one-component systems having blocked isocyanate groups or blocked amino groups, such as those used in powder coatings, coil coatings, electrodeposition coatings and liquid coatings; epoxy resins-polyurethane-hybrid systems; cyanate ester resins Compositions; and silane group-containing compositions.

  Particularly advantageous is the use in silane group-containing compositions, in which case they tend to cure rapidly even at relatively low catalyst concentrations, resulting in disadvantages due to migration such as separation, bleeding, or substrate contamination. There is no.

  The present invention therefore also relates to the use of the catalyst of formula (I) as a crosslinking catalyst in curable compositions, in particular silane group-containing compositions.

  The curable composition is then in particular an adhesive, a sealing material or a coating material.

  Another subject of the invention is a curable composition containing at least one catalyst of formula (I) as described above.

  Such compositions contain inter alia at least one epoxy resin or at least one polyisocyanate or at least one blocked isocyanate or at least one cyanester resin or at least one silane group-containing polymer.

  Preferably, the curable composition contains at least one silane group-containing polymer.

（式中、
Ｒ、Ｒ’およびＲ’’は、互いに独立してそれぞれ、炭素数１〜１２の１価の炭化水素基を表し；
Ｘは、ヒドロキシル基、または炭素数１〜１３のアルコキシ基、アセトキシ基、ケトキシマト基、アミド基、もしくはエノキシ基を表し；
ａは、０、１または２を表し；
ｍは、５０〜約２，５００の範囲の整数を表す）
を有する、末端シラン基を有するポリオルガノシロキサンである。 The silane group-containing polymer, in one embodiment, is preferably of formula (III)

(Where
R, R ′ and R ″ each independently represent a monovalent hydrocarbon group having 1 to 12 carbon atoms;
X represents a hydroxyl group or an alkoxy group having 1 to 13 carbon atoms, an acetoxy group, a ketoxymato group, an amide group, or an enoxy group;
a represents 0, 1 or 2;
m represents an integer in the range of 50 to about 2,500)
A polyorganosiloxane having a terminal silane group.

  R preferably represents methyl, vinyl or phenyl.

  R ′ and R ″ preferably each independently represent an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, especially methyl.

  X preferably represents a hydroxyl group, or an alkoxy group or ketoximato group having 1 to 6 carbon atoms, especially a hydroxyl group, a methoxy group, an ethoxy group, a methylethylketoxymato group, or a methylisobutylketoxymato group.

  Particularly preferably X represents a hydroxyl group.

  a preferably represents 0 or 1, especially 0.

  Furthermore, m is preferably selected such that the viscosity of the polyorganosiloxane of formula (III) is in the range from 100 to 500,000 mPa · s, especially from 1000 to 100,000 mPa · s at room temperature.

  Such polyorganosiloxanes are easy to handle and crosslink with moisture and / or silane crosslinkers to give solid silicone polymers with elasticity.

  Suitable commercially available polyorganosiloxanes are available, for example, from Wacker, Momentive Performance Material, GE Advanced Materials, Dow Corning, Bayer, or Shin Estu.

Preferably, the curable composition comprises, in addition to the polyorganosiloxane having a terminal silane group, a silane crosslinker, in particular of formula (IV)
(R ''') _q- Si- (X') _4-q (IV)
(Where
R ′ ″ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms;
X ′ represents a hydroxyl group or an alkoxy group having 1 to 13 carbon atoms, an acetoxy group, a ketoxymato group, an amide group, or an enoxy group;
q represents a value of 0, 1 or 2, especially 0 or 1)
Containing silane.

  Particularly suitable silanes of formula (IV) are methyltrimethoxysilane, ethyltrimethoxysilane, propitrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, tetramethoxysilane, Tetraethoxysilane, methyltris (methylethylketoximo) silane, vinyltris (methylethylketoximo) silane and methyltris (isobutylketoximo) silane.

  In a preferred embodiment of the present invention, the silane group-containing polymer is a silane group-containing organic polymer, especially a polyolefin, polyester, polyamide, poly (meth) acrylate or polyether each having one or preferably a plurality of silane groups, Or it is a mixed type (Mischform) of these polymers. The silane group may be present in the side chain or at the end, and may be bonded to the organic polymer via a C atom.

  Particularly preferably, the silane group-containing organic polymer is a silane group-containing polyolefin, a silane group-containing polyester, a silane group-containing poly (meth) acrylate, a silane group-containing polyether, or a mixed type of these polymers. Most preferred are silane group-containing polyethers.

（式中、
Ｒ^７は、炭素数１〜５の直鎖または分岐鎖の１価の炭化水素基、とりわけメチルまたはエチルまたはイソプロピルを表し；
Ｒ^８は、炭素数１〜８の直鎖または分岐鎖の１価の炭化水素基、とりわけメチルまたはエチルを表し；
ｘは、０または１または２の値、好ましくは０または１、とりわけ０を表す）
の末端基である。 Preferred as the silane group of the organic polymer is an alkoxysilane group, especially of formula (V)

(Where
R ⁷ represents a linear or branched monovalent hydrocarbon group having 1 to 5 carbon atoms, particularly methyl, ethyl or isopropyl;
R ⁸ represents a linear or branched monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly methyl or ethyl;
x represents a value of 0 or 1 or 2, preferably 0 or 1, especially 0)
It is a terminal group.

Particularly preferably R ⁷ represents methyl or ethyl.

For certain applications, the group R ⁷ preferably represents an ethyl group, since ecologically and toxicologically innocuous ethanol is eliminated upon curing of the composition.

  Particularly preferred is a trimethoxysilane group, a dimethoxymethylsilane group, or a triethoxysilane group.

  In that case, the methoxysilane group has the advantage of being particularly reactive, and the ethoxysilane group has the advantage of being toxicologically advantageous and in particular having storage stability.

  The silane group-containing organic polymer preferably has an average of 1.3 to 4, particularly 1.5 to 3, particularly preferably 1.7 to 2.8 silane groups per molecule. The silane group is preferably terminal.

  The silane group-containing organic polymer has an average molecular weight determined by GPC with respect to a polystyrene standard substance, preferably in the range of 1000 to 30,000 g / mol, especially 2000 to 20,000 g / mol. The silane equivalent of the silane group-containing organic polymer is preferably 300 to 25,000 g / Eq, particularly 500 to 15,000 g / Eq.

  The silane group-containing organic polymer may exist as a solid or liquid at room temperature. Preferably it is a liquid at room temperature.

  Most preferably, the silane group-containing organic polymer is a silane group-containing polyether which is liquid at room temperature, the silane groups being in particular dialkoxysilane groups and / or trialkoxysilane groups, particularly preferably trimethoxysilane groups or triethoxysilanes. Silane group.

  Methods for producing silane group-containing polyethers are known to those skilled in the art.

  In one method, silane group-containing polyethers can be obtained by reacting alkyl group-containing polyethers with hydrosilanes, optionally chain extended with, for example, diisocyanates.

  In another method, a silane group-containing polyether can be obtained by copolymerizing an alkylene oxide and an epoxy silane, optionally chain extended with, for example, diisocyanate.

  In another method, silane group-containing polyethers can be obtained by reacting polyether polyols with isocyanatosilanes, optionally chain extended with diisocyanates.

  In another method, the silane group-containing polyether is an isocyanate group-containing polyether, in particular an NCO-terminated urethane-polyether obtained by reacting a polyether polyol with a stoichiometric excess of polyisocyanate, an aminosilane, It can be obtained by reacting with hydroxysilane or mercaptosilane. A silane group-containing polyether obtained by this method is particularly preferred. This method allows the use of many commercially available and inexpensive starting materials, thereby obtaining different polymer properties such as high extensibility, high strength, low elastic modulus, low glass transition point or high weather resistance. be able to.

  Particularly preferably, the silane group-containing polyether can be obtained by reacting an NCO-terminated urethane-polyether with aminosilane or hydroxysilane. Suitable NCO-terminated urethane-polyethers include polyether polyols, especially polyoxyalkylene diols or polyoxyalkylene triols, preferably polyoxypropylene diols or polyoxypropylene triols, in stoichiometric excess polyisocyanates, especially It can be obtained by reacting with diisocyanate.

  Preferably, the reaction between the polyisocyanate and the polyether polyol is carried out under anhydrous conditions at a temperature between 50 ° C. and 160 ° C., optionally in the presence of a suitable catalyst, in which case the polyisocyanate has its isocyanate group. Is provided in a stoichiometric excess compared to the hydroxyl groups of the polyol. In particular, the excess polyisocyanate has a content of free isocyanate groups of 0.1 to 5% by weight, based on the total polymer, in the urethane-polyether obtained after all hydroxyl groups have reacted. It is preferably selected to be 0.2 to 4% by weight, particularly preferably 0.3 to 3% by weight.

  Preferred diisocyanates are 1,6-hexamethylene diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (= isophorone diisocyanate or IPDI), 2,4- and 2,6. -Toluylene diisocyanate and any mixture of these isomers (TDI) and 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate, and any mixture of these isomers (MDI) ). Particularly preferred is IPDI or TDI. Most preferred is IPDI. Accordingly, a silane group-containing polyether having particularly good light resistance can be obtained.

  Particularly suitable as polyether polyols are those with an unsaturation below 0.02 mEq / g, especially below 0.01 mEq / g and an average molecular weight of 400-25,000 g / mol, especially 1000-20,000 g. Polyoxyalkylene diol or polyoxyalkylene triol in the range of / mol.

  Besides polyether polyols, other polyols, in particular polyacrylate polyols, as well as low molecular weight diols or triols can be used accordingly.

  Suitable aminosilanes for reaction with NCO-terminated urethane-polyethers are primary and secondary aminosilanes. Preferred is 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-aminobutyl-trimethoxysilane, 4-amino-3-methylbutyl-trimethoxysilane, 4-amino-3,3-dimethyl. Butyl-trimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, primary aminosilane, such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxy Methylsilane or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and a Michael acceptor such as acrylonitrile, (meth) acrylic acid ester, (meth) acrylic acid amide, maleic acid diester or fumaric acid Diester, shi Rakon acid diester or an adduct of itaconic acid diesters, especially N- (3- trimethoxysilylpropyl) amino - succinic acid diethyl ester - dimethyl succinate ester or N- (3- trimethoxysilylpropyl) amino. Also suitable are analogs of the aforementioned aminosilanes having ethoxy or isopropoxy groups on silicon instead of methoxy groups.

  Hydroxysilanes suitable for reaction with NCO-terminated urethane-polyethers can be obtained, inter alia, by adding aminosilanes to lactones or cyclic carbonates or lactides.

  Suitable aminosilanes include 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 4-aminobutyl-trimethoxysilane, 4-aminobutyl-triethoxysilane, 4-amino-3-methylbutyl, among others. -Trimethoxysilane, 4-amino-3-methylbutyl-triethoxysilane, 4-amino-3,3-dimethylbutyl-trimethoxysilane, 4-amino-3,3-dimethylbutyl-triethoxysilane, 2-amino Ethyl-trimethoxysilane or 2-aminoethyl-triethoxysilane. Particularly preferred are 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 4-amino-3,3-dimethylbutyl-trimethoxysilane, or 4-amino-3,3-dimethylbutyl- Triethoxysilane.

  Suitable as lactones are especially γ-valerolactone, γ-octalactone, δ-decalactone, and ε-decalactone, especially γ-valerolactone.

  Particularly suitable as cyclic carbonates are 4,5-dimethyl-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3. -Dioxolan-2-one, 4-methyl-1,3-dioxolan-2-one, or 4- (phenoxymethyl) -1,3-dioxolan-2-one.

  Suitable as lactide are, in particular, 1,4-dioxane-2,5-dione (lactide obtained from 2-hydroxyacetic acid, also called “glycolide”), 3,6-dimethyl-1,4-dioxane. -2,5-dione (lactide obtained from lactic acid, also referred to as "lactide") and 3,6-diphenyl-1,4-dioxane-2,5-dione (lactide obtained from mandelic acid).

  Preferred hydroxysilanes thus obtained are N- (3-triethoxysilylpropyl) -2-hydroxypropanamide, N- (3-trimethoxysilylpropyl) -2-hydroxypropanamide, N- (3- Triethoxysilylpropyl) -4-hydroxypentanamide, N- (3-triethoxysilylpropyl) -4-hydroxyoctanamide, N- (3-triethoxysilylpropyl) -5-hydroxydecanamide and N- (3 -Triethoxysilylpropyl) -2-hydroxypropyl carbamate.

  Furthermore, suitable hydroxysilanes can also be obtained by adding aminosilanes to epoxides or by adding amines to epoxysilanes.

  Preferred hydroxysilanes thus obtained are 2-morpholino-4 (5)-(2-trimethoxysilylethyl) cyclohexane-1-ol, 2-morpholino-4 (5)-(2-triethoxysilylethyl). ) Cyclohexane-1-ol, or 1-morpholino-3- (3- (triethoxysilyl) propoxy) propan-2-ol.

Silane group-containing polyethers include commercially available products, in particular: MS Polymer ™ (manufactured by Kaneka Corporation; especially types S203H, S303H, S227, S810, MA903 and S943); MS Polymer ™ or Sylyl (Trademark) (manufactured by Kaneka Co., Ltd .; especially type SAT010, SAT030, SAT200, SAX350, SAX400, SAX725, MAX450, MAX951); Excestar (registered trademark) (manufactured by Asahi Glass Co., Ltd .; SPUR ⁺ * (Momentive Performance Materials, Ltd., among other things type 1010LM, 1015LM, 1050MM); Vorasil ( trademark (Dow Chemical Co .; especially types 602 and 604); Desmosal (R) (from Bayer MaterialScience AG; especially types S XP 2458, S XP 2636, S XP 2749, S XP 2774 and S XP 2821, TE OP 2821) Registered trademark) (Evonik Industries AG; especially type Seal 100, Bond 150, Bond 250), Polymer ST (manufactured by Hanse Chemie AG / Evonik Industries AG, especially types 47, 48, 61, 61LV, 77, 80, 81); Geniosil® STP (from Wacker Chemie AG; types E10, E15, E30, E35, among others) Is suitable.

｛式中、
Ｒ^９は、場合により環状および／または芳香族の部分および場合により１個または複数個のヘテロ原子、とりわけ１個または複数個の窒素原子を有する炭素数１〜１２の直鎖または分岐鎖の２価の炭化水素基を表し；
Ｙは、−Ｏ−、−Ｓ−、−Ｎ（Ｒ^１０）−、−Ｏ−ＣＯ−Ｎ（Ｒ^１０）−、−Ｎ（Ｒ^１０）−ＣＯ−Ｏ−および−Ｎ（Ｒ^１０）−ＣＯ−Ｎ（Ｒ^１０）−
（式中、Ｒ^１０は、水素、または場合により環状部分を有し、場合によりアルコキシシリル基、エーテル基、またはカルボン酸エステル基を有する炭素数１〜２０の直鎖もしくは分岐鎖の炭化水素基を表す）
から選択される２価の基を表し；
Ｒ^７、Ｒ^８およびｘは前述の意味を有する｝
の末端基である。 Particularly preferred end groups of formula (V) are those of formula (VI)

{Where
R ⁹ is an optionally substituted cyclic and / or aromatic moiety and optionally one or more heteroatoms, in particular one or more nitrogen atoms, straight chain or branched 2 having 1 to 12 carbon atoms. Represents a divalent hydrocarbon group;
Y represents —O—, —S—, —N (R ¹⁰ ) —, —O—CO—N (R ¹⁰ ) —, —N (R ¹⁰ ) —CO—O— and —N (R ¹⁰ ) —. CO-N ^{(R 10)} -
(Wherein R ¹⁰ is hydrogen or an optionally substituted cyclic moiety, and optionally an alkoxysilyl group, an ether group, or a carboxylic acid ester group having a C 1-20 linear or branched hydrocarbon group. Represents)
Represents a divalent group selected from:
R ⁷ , R ⁸ and x have the aforementioned meanings}
It is a terminal group.

Preferably, R ⁹ represents 1,3-propylene or 1,4-butylene, which may be substituted with 1 or 2 methyl groups.

Particularly preferably R ⁹ is 1,3-propylene.

  Preferably, the catalyst of formula (I) is in an amount such that the weight ratio of the silane group-containing polymer to the catalyst of formula (I) is 10/1 or more, preferably 20/1 or more in the silane group-containing composition. Exists.

  More preferably, the catalyst of formula (I) has a weight ratio of silane group-containing polymer to catalyst of formula (I) in the silane group-containing composition of 5,000 / 1 or less, preferably 2,000 / 1 or less. In particular, it is present in an amount such that it is 1,000 / 1 or less.

  Preferably, the weight ratio of the silane group-containing polymer to the catalyst of formula (I) is in the range of 10/1 to 2,000 / 1, especially 20/1 to 2,000 / 1.

  Such compositions have a sufficient shelf life and cure rapidly.

  In addition to the catalyst of formula (I), the curable composition may contain other catalysts, in particular catalysts for crosslinking silane groups. Suitable as other catalysts are inter alia metal catalysts and / or basic nitrogen compounds or phosphorus compounds.

  Possible metal catalysts are inter alia tin, titanium, zirconium, aluminum or zinc compounds, in particular diorganotin (IV) compounds, such as in particular dibutyltin (IV) diacetate, dibutyltin (IV) dilaurate, dibutyltin (IV) di Neodecanoate, or dibutyltin (IV) bis (acetylacetonate), and dioctyltin (IV) dilaurate, and titanium (IV) complex or zirconium (IV) complex or aluminum (III) complex or zinc (II) complex, In particular, it is a complex with an alkoxy ligand, a carboxylate ligand, a 1,3-diketonate ligand, a 1,3-ketoesterate ligand, or a 1,3-ketoamidate ligand.

  Possible basic nitrogen or phosphorus compounds are inter alia imidazole, pyridine, phosphazene base or preferably amines, hexahydrotriazines or biguanides, and amidines or guanidines not corresponding to formula (I).

Suitable amines are inter alia alkylamines, cycloalkylamines or aralkylamines such as triethylamine, triisopropylamine, 1-butylamine, 2-butylamine, tert-butylamine, 3-methyl-1-butylamine, 3-methyl-2 -Butylamine, dibutylamine, tributylamine, hexylamine, dihexylamine, cyclohexylamine, dicyclohexylamine, dimethylcyclohexylamine, benzylamine, dibenzylamine, dimethylbenzylamine, octylamine, 2-ethylhexylamine, di- (2-ethylhexyl) ) Amine, laurylamine, N, N-dimethyllaurylamine, stearylamine, N, N-dimethyl-stearylamine; , For example, especially coconut oil alkyl amine, N, N-dimethyl - cocoalkyl _{amine, C 16 to 22} - alkylamines, N, N-dimethyl _{-C 16 to 22} - alkylamines, soybean alkylamine, N, N -Dimethyl-soybean oil alkylamine, oleylamine, N, N-dimethyl-oleylamine, tallow alkylamine or N, N-dimethyl-tallow alkylamine, for example Armeen (R) (from Akzo Nobel) or Rofamine (R) Available under the trade name (from Ecogreen Oleochemicals); aliphatic, cycloaliphatic or araliphatic diamines such as ethylenediamine, butanediamine, hexamethylenediamine, dodecanediamine, neopentanediamine, 2-methyl-pentamethene Range amine (MPMD), 2,2 (4), 4-trimethylhexamethylenediamine (TMD), isophoronediamine (IPD), 2,5 (2,6) -bis- (aminomethyl) -bicyclo [2.2 .1] Heptane (NBDA), 1,3-xylenediamine (MXDA), N, N′-di (tert-butyl) ethylenediamine, N, N, N ′, N′-tetramethyl-ethylenediamine, N, N, N ′, N′-tetramethyl-propylenediamine, N, N, N ′, N′-tetramethyl-hexamethylenediamine, 3-dimethylaminopropylamine, 3- (methylamino) propylamine, 3- (cyclohexylamino) ) Propylamine, piperazine, N-methylpiperazine, N, N'-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octa Fatty polyamines such as N-coconut oil alkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-soybean oil alkyl-1,3-propanediamine, N-tallow alkyl-1, 3-propanediamine, or _{N- (C 16~22} - alkyl) -1,3-propanediamine, for example, Duomeen (R) those available under the trade name (Akzo Ltd. Nobel); polyalkylene amine, for example, Diethylenetriamine, dipropylenetriamine, triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentamethylenehexamine (PEHA), 3- (2-aminoethyl) aminopropylamine, N, N′-bis (3-amino Propyl) ethylenediamine, N- (3-aminopropyl)- -Methylpropanediamine, bis (3-dimethylaminopropyl) amine, N- (3-dimethylaminopropyl) -1,3-propylenediamine, N- (2-aminoethyl) piperazine (N-AEP), N- ( 2-aminopropyl) piperazine, N, N′-di- (2-aminoethyl) piperazine, 1-methyl-4- (2-dimethylaminoethyl) piperazine, N, N, N ′, N ″, N ″ — Pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, polyethyleneimine such as Lupasol (registered trademark) (manufactured by BASF) and Epomin (registered trademark) (manufactured by Nippon Shokubai Co., Ltd.) Available under the trade name; ether amines, such as 2-methoxyethylamine, 2-ethoxyethylamine, among others , 3-methoxypropylamine, 3-ethoxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3- (2-methoxyethoxy) propylamine, 2 (4) -methoxyphenylethylamine, morpholine, N-methyl Morpholine, N-ethylmorpholine, 2-aminoethylmorpholine, bis (2-aminoethyl) ether, bis (dimethylaminoethyl) ether, bis (dimorpholinoethyl) ether, N, N, N'-trimethyl-N'- Hydroxyethylbis (2-aminoethyl) ether, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7-dioxadecane-2,9-diamine, 4 , 9-Dioxadodecane-1,12-diamine, 5,8-Dioxadodecane- , 10-diamine, 4,7,10-trioxatridecane-1,13-diamine or 2-aminopropyl-terminated glycol, such as those available under the trade name Jeffamine® (from Huntsman); Alcohols such as, inter alia, ethanolamine, isopropanolamine, diethanolamine, diisopropanolamine, triethanolamine, triisopropanolamine, N-butylethanolamine, diglycolamine, N, N-diethylethanolamine, N-methyldiethanolamine, N- Methyldiisopropylamine, N, N, N′-trimethylaminoethylethanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N, N-bis (3-dimethylamine) Nopropyl) -N-isopropanolamine, 2- (2-dimethylaminoethoxy) ethanolamine, or adducts of monoamines and polyamines with epoxides or diepoxides; phenol group-containing amines such as, inter alia, phenols, aldehydes, amines ( Condensation products obtained from so-called Mannich base and phenalkamine, for example 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, or phenol, formaldehyde and N, N -Polymers obtained from dimethyl-1,3-propanediamine, and Cardolite (R) (from Cardolite), Aradur (R) (from Huntsman) and Beckopox ( Phenalkamine commercially available under the trade name of Cytec; amide group-containing polyamines, so-called polyamidoamines, such as Versamid® (from Cognis), Aradur® (from Huntsman), Euretek ( (Registered trademark) (manufactured by Huntsman) or Beckopox (registered trademark) (manufactured by Cytec); or aminosilanes such as 3-aminopropyltrimethoxysilane, especially 3-aminopropyldimethoxymethylsilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -N '-[3- (tri Methoxysilyl) propyl] Diamine, or an analogue having ethoxy groups in place of methoxy groups on the silicon.

  Suitable triazines are especially 1,3,5-hexahydrotriazine or 1,3,5-tris (3- (dimethylamino) propyl) -hexahydrotriazine.

  Suitable biguanides are inter alia biguanides, 1-butyl biguanide, 1,1-dimethyl biguanide, 1-butyl biguanide, 1-phenyl biguanide or 1- (o-toluyl) biguanide (OTBG).

  Suitable amidines not corresponding to formula (I) are especially 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0] non-5- Ene (DBN), 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene, 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene N, N′-di-n-hexylacetamidine (DHA), 2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 2 , 5,5-trimethyl-1,4,5,6-tetrahydropyrimidine, N- (3-trimethoxysilylpropyl) -4,5-dihydroimidazole or N- (3-triethoxysilylpropyl)- , 5-dihydro-imidazole.

  Suitable guanidines not corresponding to formula (I) are especially 1-butylguanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1,1,3,3-tetramethylguanidine (TMG), 2- ( 3- (trimethoxysilyl) propyl) -1,1,3,3-tetramethylguanidine, 2- (3- (methyldimethoxysilyl) propyl) -1,1,3,3-tetramethylguanidine, 2- ( 3- (triethoxysilyl) propyl) -1,1,3,3-tetramethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl -1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, -Phenylguani Emissions, 1-(o-tolyl) guanidine (OTG), 1,3-diphenylguanidine, 1,3-di (o-tolyl) guanidine, or 2-guanidino-benzimidazole.

  Furthermore, the curable composition can contain acids, especially carboxylic acids, as cocatalysts. Preference is given to saponification of aliphatic carboxylic acids such as formic acid, lauric acid, stearic acid, isostearic acid, oleic acid, 2-ethyl-2,5-dimethylcaproic acid, 2-ethylhexanoic acid, neodecanoic acid, natural fats and oils Or a dicarboxylic acid and a polycarboxylic acid, especially poly (meth) acrylic acid.

  In a preferred embodiment, the curable composition is substantially free of organotin compounds. Organotin-free compositions are advantageous for health protection and environmental protection. In particular, the tin content of the curable composition is less than 0.1% by weight, in particular less than 0.05% by weight.

  In one embodiment of the invention, the curable composition further contains at least one organotitanate in addition to the catalyst of formula (I). The combination of the catalyst of formula (I) and the organotitanate has a particularly high catalytic activity. Thereby, rapid curing of such compositions is possible even if the amount of catalyst of formula (I) used is relatively small.

  Particularly suitable as organotitanates are titanium (IV) complex compounds.

Preferred organotitanates are titanium (IV) complex compounds having inter alia -2,1,3-diketonate ligands, in particular 2,4-pentandionate (= acetylacetonate) and two alcoholate ligands. ;
-A titanium (IV) complex compound having two 1,3-ketoesterate ligands, in particular ethyl acetoacetate and two alcoholate ligands;
Titanium (IV) complexes having one or more amino alcoholate ligands, especially triethanolamine or 2-((2-aminoethyl) amino) ethanol, and one or more alcoholate ligands Compound;
A titanium (IV) complex compound having -4 alcoholate ligands;
As well as relatively highly condensed organic titanates, in particular oligomeric titanium (IV) -tetrabutanolates, also called polybutyl titanates;
Selected from
As alcoholate ligands, isobutoxy, n-butoxy, isopropoxy, ethoxy and 2-ethylhexoxy are particularly suitable.

  Particularly suitable are commercially available types Tyzor® AA, GBA, GBO, AA-75, AA-65, AA-105, DC, BEAT, BTP, TE, TnBT, KTM, TOT, TPT or IBAY (All from Dorf Ketal); Tytan PBT, TET, X85, TAA, ET, S2, S4 or S6 (all from Borica Company Ltd.), and Ken-React® KR® TTS, 7, 9QS 12, 26S, 33DS, 38S, 39DS, 44, 134S, 138S, 133DS, 158FS or LICA (registered trademark) 44 (all manufactured by Kenrich Petrochemicals).

  Particularly very suitable organic titanates are bis (ethylacetoacetate) diisobutoxy-titanium (IV) (for example, commercially available from Dorf Ketal as Tyzor® IBAY), bis (ethylacetoacetate) diiso Propoxy-titanium (IV) (eg commercially available from Dorf Ketal as Tyzor® DC), bis (acetylacetato) diisopropoxy-titanium (IV), bis (acetylacetato) diisobutoxy-titanium (IV), Tris (Oxyethyl) amine-isopropoxy-titanium (IV), bis [tris (oxyethyl) amine] diisopropoxy-titanium (IV), bis (2-ethylhexane-1,3-dioxy) -titanium (IV), tris [2-((2-aminoethyl) a Mino) ethoxy] ethoxy-titanium (IV), bis (neopentyl (diallyl) oxy) -diethoxy-titanium (IV), titanium (IV) -tetrabutanolate, tetra (2-ethylhexyloxy) titanate, tetra (isopropoxy) ) Selected from titanate and polybutyl titanate.

  Most preferred is bis (ethylacetoacetate) diisobutoxy-titanium (IV) or bis (ethylacetoacetate) diisopropoxy-titanium (IV).

  In the organotitanate-containing composition, the weight ratio of the silane group-containing polymer to the catalyst of formula (I) is preferably in the range of 20/1 to 2,000 / 1, especially 40/1 to 2,000 / 1.

  The weight ratio of the organotitanate to the catalyst of the formula (I) is preferably in the range from 10/1 to 1/10, particularly preferably from 5/1 to 1/5, especially from 5/1 to 1/3.

In addition to the catalyst of formula (I), the curable composition comprises other components, especially the following auxiliaries and additives:
Adhesion promoters and / or crosslinkers, especially aminosilanes, such as especially 3-aminopropyl-trimethoxysilane, 3-aminopropyl-dimethoxymethylsilane, N- (2-aminoethyl) -3-aminopropyl-trimethoxy Instead of silane, N- (2-aminoethyl) -3-aminopropyl-dimethoxymethylsilane, N- (2-aminoethyl) -N ′-[3- (trimethoxysilyl) propyl] ethylenediamine, or methoxy group Analogs thereof having an ethoxy group, N-phenylsilane, N-cyclohexylsilane, or N-alkylaminosilane, mercaptosilane, epoxysilane, (meth) acrylosilane, anhydridosilane, carbamatosilane, alkylsilane or iminosilane, these Silane In the form of oligomers, adducts of primary aminosilanes with epoxy silanes or (meth) acrylosilanes or anhydride silanes, aminofunctional alkylsilsesquioxanes, especially aminofunctional methylsilsesquioxanes or aminofunctional propylsilsesquioxanes Oxan. Particularly suitable are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3. -Aminopropyl-triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane or 3-ureidopropyltrimethoxysilane, or oligomers of these silanes;
A desiccant, in particular tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or an organoalkoxysilane having a functional group in the α-position relative to the silane group, in particular N- (methyldimethoxysilylmethyl) -O-methyl- Carbamate, (methacryloxymethyl) silane, methoxymethylsilane, orthoformate, calcium oxide or molecular sieve, especially vinyltrimethoxysilane or vinyltriethoxysilane;
-Plasticizers, especially trialkylsilyl-terminated polydialkylsiloxanes, such as especially trimethylsilyl-terminated polydimethylsiloxanes, especially those with viscosities in the range of 10 to 1,000 mPa · s, or some of the methyl groups are other organic groups, especially Corresponding compounds substituted by phenyl, vinyl or trifluoropropyl groups, so-called monofunctional and therefore reactive plasticizers in the form of polysiloxanes which are reactive on one side, carboxylic acid esters, for example phthalic acid Esters, especially dioctyl phthalate, bis (2-ethylhexyl) phthalate, bis (3-propylheptyl) phthalate, diisononyl phthalate or diisodecyl phthalate, diesters of ortho-cyclohexanedicarboxylic acid, especially diisononyl-1,2-cyclohexane Sandicarboxylate, adipic acid ester, especially dioctyl adipate, bis (2-ethylhexyl) adipate, azelaic acid ester, especially bis (2-ethylhexyl) acetate, sebacic acid ester, especially bis (2-ethylhexyl) sebacate or sebacin Fatty acid methyl from natural fats, also called diisononyl acids, polyols, especially polyoxy-alkylene polyols or polyester polyols, glycol ethers, glycol esters, organophosphate esters or sulfonate esters, sulfonate amides, polybutenes, or “biodiesel” Ester or fatty acid ethyl ester, siloxane group-containing plasticizer is suitable for silane group-containing polymer in the form of polyorganosiloxane Plasticizer;
-Solvent;
-Natural or ground or precipitated calcium carbonate, barite, talc, quartz sand powder, quartz sand, optionally coated with inorganic or organic fillers, especially fatty acids, especially stearic acid, Dolomite, wollastonite, kaolin, calcined kaolin, mica (potassium aluminum silicate), molecular sieve, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silicic acid containing highly dispersible silicic acid by pyrolysis, industrially Produced carbon black, graphite, metal powder, for example, powders such as aluminum, copper, iron, silver or steel, PVC powder or hollow spheres;
-Fibers, especially glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers, for example polyamide fibers or polyethylene fibers;
-Colorants;
Pigments, especially titanium dioxide or iron oxide;
-Rheology modifiers, especially thickeners, especially layered silicates such as bentonite, castor oil derivatives, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, pyrogenic silicic acid, cellulose ethers or hydrophobically modified polyoxyethylene ;
-Stabilizers against oxidation, heat, light or UV;
-Natural resins, oils and fats such as rosin, shellac, linseed oil, castor oil or soybean oil;
A non-reactive polymer, for example a homopolymer or copolymer of an unsaturated monomer, especially an unsaturated monomer homopolymer selected from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates Or a copolymer, especially polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene vinyl acetate copolymer (EVA) or atactic poly-α-olefin (APAO);
Flame retardant materials, especially the aforementioned fillers aluminum hydroxide and magnesium hydroxide, or especially organic phosphate esters, such as, inter alia, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, Isodecyl diphenyl phosphate, tris phosphate (1,3-dichloro-2-propyl), tris phosphate (2-dichloroethyl), tris phosphate (2-ethylhexyl), tris phosphate (dichloroisopropyl), phosphoric acid Tris (dichloropropyl), isopropylated triphenyl phosphate, mono (isopropylphenyl) phosphate of various degrees of isopropylation, bis (isopropylphenyl) phosphate, or tris (isopropylphenyl) phosphate, resorcinol-bis (diphenyl phosphate) ), Bisuf Nord -A- bis (diphenyl phosphate), or ammonium polyphosphate;
-Surface active substances, in particular wetting agents, leveling agents, defoaming agents or antifoaming agents;
-Biocides, especially algicides, fungicides, or fungal growth inhibitors;
Moreover, you may contain the other substance normally used for a curable composition. It may be useful to dry certain components chemically or physically prior to mixing into the composition.

  In a preferred embodiment, the curable composition contains at least one desiccant and at least one adhesion promoter and / or crosslinker.

  In a preferred embodiment, the curable composition does not contain a phthalate ester as a plasticizer. Such compositions are toxicologically advantageous and have fewer problems with migration phenomena.

  The curable composition is preferably prepared and stored under anhydrous conditions. Typically it is storage-stable under anhydrous conditions in a suitable packaging or arrangement, for example in bottles, cans, bags, pail cans, barrels or cartridges, among others.

  The curable composition may be present in the form of a one-component composition or may be present in the form of a multi-component composition, especially in the form of a two-component composition.

  “One component system” as used herein refers to a composition in which all components of the composition are stored mixed in the same container and cured with moisture.

  “Two-component system” as used herein refers to a composition that exists as two different components in which the components of the composition are stored in separate containers. Only before or during the application of the composition, the two components are mixed together, after which the mixed composition is optionally cured by the action of moisture.

  Curable compositions are used in many applications, especially as paints, lacquers or primers, as resins for the production of fiber composites (composites), as rigid foams, flexible foams, molded articles, elastomers, fibers, films or films, As casting and sealing materials, sealing materials, adhesives, coatings, coating materials or paints for construction and industrial use, for example, seam seals, car body rust sealants, electrical insulation materials, putty materials, joint sealing materials, welding Seam sealing material or flange edge welding sealing material, assembly adhesive, car body adhesive, window glass adhesive, sandwich structural member adhesive, lamination adhesive, laminating adhesive, packaging adhesive, wood adhesive, flooring Adhesives, fixing adhesives, floor coverings, floor coatings , Balcony coatings, roof coatings, concrete protective coating, parking coatings, sealants, pipe coatings, anticorrosive coatings, textile coatings, cushioning members, are suitable as a sealing member or putty.

  Curable composition is used as an adhesive and / or sealing material, in particular for joint sealing and as an adhesive and / or sealing material for elastic adhesive bonding in construction and industrial applications, and an elastic coating material having crack crosslinkability As a particular example, it is particularly suitable for the protection and / or sealing of roofs, floors, balconies, parking building levels or concrete pipes, for example.

  Such compositions typically contain plasticizers, fillers, adhesion promoters and / or crosslinkers and desiccants, and optionally other auxiliaries and additives.

  For use as an adhesive or sealant, the curable composition preferably has a paste consistency and is structurally viscous. Such paste-like sealants or adhesives are based on, inter alia, manually, from commercial cartridges operating on compressed air or batteries, or from barrels or transport tins, with feed pumps or extruders, optionally with application robots. It is applied on the material.

  For use as a coating material, the curable composition preferably has a liquid consistency at room temperature and is self-leveling. In some cases it is slightly thixotropic so that the coating material can be applied to steep to vertical surfaces without dripping immediately. It is applied, inter alia, by rolling or brushing or by pouring and spreading with, for example, a roller, a doctor blade or a scissors.

  Furthermore, the present invention relates to a cured composition which can be obtained after curing from a curable composition containing at least one catalyst of formula (I) as described above. Curing takes place in particular with water, in particular with water in the form of moisture in the air, and / or with a suitable crosslinking agent.

  The use of a curable composition results in articles that are especially bonded, sealed or coated with the composition. Articles include, inter alia, buildings, especially ground or underground structures, industrial products, or consumer goods, especially windows, household equipment or means of transportation, such as cars, buses, trucks, rail vehicles, ships, airplanes, among others. Or a helicopter; or the article may be its attachment.

  Preferred curable compositions contain at least one silane group-containing polymer. Such compositions are also referred to below as “silane crosslinkable compositions”.

  Usually, the proportion of the silane group-containing polymer in the silane crosslinkable composition is 10 to 80% by weight, especially 15 to 60% by weight, preferably 15 to 50% by weight, based on the total weight of the composition.

  When the silane crosslinkable composition contains a polyorganosiloxane having a terminal silane group, not only a one-component composition also called RTV-1 but also a two-component composition called RTV-2 preferable. In the case of RTV-2 compositions, the polyorganosiloxane having terminal silane groups is preferably a component of the first component, and the silane crosslinker, especially the silane of formula (IV), is preferably a component of the second component. It is. The catalyst of formula (I) may then be contained in the first component and / or the second component.

  When the silane crosslinkable composition contains a silane group-containing organic polymer, the composition is preferably a one-component system.

  The second component or optionally other components are mixed with the first component before or during application, in particular in a static mixer or in a dynamic mixer.

  The silane crosslinkable composition is applied, especially at ambient temperature, preferably in the temperature range of 0 to 45 ° C., especially 5 to 35 ° C. and cures under these conditions.

  At the time of application, the crosslinking reaction of the silane group may start under the influence of moisture. The existing silane group can be condensed with the existing silanol group to become a siloxane group (Si-O-Si group). The existing silane group can also be hydrolyzed to a silanol group (Si—OH group) upon contact with moisture, and a siloxane group (Si—O—Si group) can be formed by a subsequent condensation reaction. As a result of this reaction, the composition finally cures. The catalyst of formula (I) promotes this curing.

  If water is required for curing, this may be derived from air (moisture in the air) or by applying the composition with a water-containing component, for example, for example a smoothing agent May be contacted by applying or spraying, or adding water or water-containing ingredients to the composition at the time of application, for example in the form of a liquid or paste containing water or releasing water May be. Pastes are particularly suitable when the composition itself is present in the form of a paste.

  When cured with moisture in the air, the composition cures from the outside to the inside, at which time a film is first formed on the surface of the composition. The so-called film formation time is a measure of the cure rate of the composition. In that case, the cure rate is generally determined by various factors such as water availability, temperature, and the like.

  Silane crosslinkable compositions typically have a good shelf life with no tendency to separate, and the low toxicity and volatility of the catalyst of formula (I) allows for a low hazard classification and cures rapidly. , Which enables products with low emission and odor, which form a highly durable material with high mechanical quality. In that case, in contrast to compositions containing prior art catalysts such as, for example, DBU, TMG, or DHA, these materials tend to suffer from disadvantages due to migration such as bleed or substrate contamination. It is particularly advantageous not to. Compositions containing such prior art catalysts are prone to migration phenomena, which are in the form of separations before curing and surface tackiness and / or stickiness and / or substrate contamination after curing. May appear in shape. In particular, the latter phenomenon is very undesirable because the sticky and sticky surface is immediately contaminated, the top coatability is poor, and the substrate impurities can lead to residual coloring.

During application, the silane crosslinkable composition is preferably applied to at least one substrate.
Suitable substrates are among others
-Glass, glass ceramic, concrete, mortar, brick, roof tile, plaster, or natural stone such as limestone, granite or marble;
Metals and alloys, such as aluminum, iron, steel, or non-ferrous metals, and surface modified metals or alloys, such as galvanized or chrome plated metals;
-Woody materials, resin-textile composites, and other so-called polymer composites combined with leather, textiles, paper, wood, resins and eg phenolic, melamine or epoxy resins;
-Plastics, such as polyvinyl chloride (hard PVC and soft PVC), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), polyamide (PA), polyester, poly (methyl methacrylate) (PMMA), epoxy resin, Polyurethane (PUR), polyoxymethylene (POM), polyolefin (PO), polyethylene (PE), or polypropylene (PP), ethylene / propylene copolymer (EPM) or ethylene / propylene / diene terpolymer (EPDM), or fiber reinforced Plastics, such as carbon fiber reinforced plastic (CFK), glass fiber reinforced plastic (GFK), or sheet-like forming material (SMC), preferably plasma, corona, or flame Good plastic be surface-treated;
A coated substrate, for example a powder-coated metal or alloy;
Paints or lacquers, especially automotive finishes;
It is.

  The substrate can optionally be pretreated before application of the composition, in particular by physical and / or chemical cleaning methods, or by application of adhesion promoters, adhesion promoter solutions, or primers. .

  Silane crosslinkable compositions are particularly suitable for contact with substrates that are particularly prone to problems with migratory materials, especially discoloration or stain formation. These are inter alia microporous substrates such as marble, limestone or other natural stone, gypsum, cement mortar or concrete, as well as plastic. In particular, in PVC, intense discoloration is observed that cannot be removed by purification in the presence of a catalyst such as DBU or TMG. Such a phenomenon is not observed when the catalyst of the formula (I) is used.

  The silane crosslinkable composition is particularly suitable as an adhesive and / or sealing material or as a coating material.

  Two identical substrates or two different substrates, in particular the aforementioned substrates, can be glued or sealed.

  In the following, examples which describe the above-described present invention in more detail are described. Obviously, the invention is not limited to the examples described.

  “Standard atmosphere” refers to a temperature of 23 ± 1 ° C. and a relative humidity of 50 ± 5% in air.

The infrared spectrum (FT-IR) was measured with a FT-IR apparatus Nicolet iS5 manufactured by Thermo Scientific equipped with a horizontal ATR measurement unit having diamond crystals. The liquid sample was undiluted and applied as a coating, and the solid sample was dissolved in CH ₂ Cl ₂ . The absorption band is indicated by wave number (cm ⁻¹ ) (measurement range: 4000 to 650 cm ⁻¹ ).

The viscosity was measured with a conditioned cone and plate viscometer Rheotec RC30 (cone diameter 50 mm, cone angle 1 °, distance between cone tip and plate 0.05 mm, shear rate 10 s ⁻¹ ).

  Film formation time (HBZ) is the first residue when a few grams of the composition is applied on a cardboard with a film thickness of about 2 mm and the surface of the composition is lightly touched with an LDPE pipette in a standard atmosphere. Was determined by measuring the time required until no longer remained.

  The surface properties were tested by touch.

  Mechanical properties such as tensile strength, strength at break and elastic modulus (at 0-5% strain and 0-50% strain) were measured according to DIN EN 53504 at a pulling speed of 200 mm / min.

  Shore A hardness was determined on specimens cured in standard atmosphere for 7 days according to DIN 53505.

Production of the catalyst of formula (I):
Catalyst K-1: 1,1 ′-(α, ω-polyoxypropylene) bis (2,3-dicyclohexylguanidine) having a molecular weight of about 650 g / mol
In a round bottom flask, polyoxypropylenediamine having an average molecular weight of about 230 g / mol (Jeffamine (registered trademark) D-230 manufactured by Huntsman, amine content of about 8.4 meq / g), 5.49 g, and N, N′— Dicyclohexylcarbodiimide (8.26 g) was mixed, and the mixture was heated and stirred at 110 ° C. The reaction mixture was examined by FT-IR spectroscopy at regular intervals. After 22 hours, the carbodiimide absorption band at about 2120 cm ⁻¹ disappeared completely. Thereafter, volatile components were removed from the reaction mixture under reduced pressure. 13.12 g of odorless pale yellow oil was obtained.
FT-IR: 3366 (N-H), 2923, 2950, 1635 (C = N), 1495, 1447, 1370, 1336, 1255, 1237, 1102, 1025, 977, 888, 845, 713.

Catalyst K-2: 1,1 ′-(α, ω-polyoxypropylene) bis (2,3-dicyclohexylguanidine) having a molecular weight of about 850 g / mol
In a round bottom flask, polyoxypropylenediamine having an average molecular weight of about 430 g / mol (Jeffamine® D-400 manufactured by Huntsman, amine content of about 4.4 meq / g) and N, N′-dicyclohexyl The carbodiimide 8.23g was mixed and the mixture was heated and stirred at 120 degreeC. The reaction mixture was examined by FT-IR spectroscopy at regular intervals. After 24 hours, the carbodiimide absorption band of about 2120 cm ⁻¹ disappeared completely. Thereafter, volatile components were removed from the reaction mixture under reduced pressure. 18.77 g of odorless pale yellow oil having a viscosity of 12.3 Pa · s at 25 ° C. was obtained.
FT-IR: 3357 (N-H), 2968, 2924, 2951, 1637 (C = N), 1498, 1448, 1372, 1340, 1256, 1237, 1100, 1018, 926, 889, 845, 715.

Catalyst K-3: 1- (ω-methoxy-polyoxypropylene-polyoxyethylene) -2,3-dicyclohexylguanidine having a molecular weight of about 810 g / mol In a round bottom flask, polyoxypropylene monoamine having an average molecular weight of about 600 g / mol 14.32 g (Jeffamine (registered trademark) M-600 manufactured by Huntsman, amine content of about 1.7 meq / g) and 4.14 g of N, N′-dicyclohexylcarbodiimide were mixed, and the mixture was heated and stirred at 120 ° C. did. The reaction mixture was examined by FT-IR spectroscopy at regular intervals. After 72 hours, the carbodiimide absorption band of about 2120 cm ⁻¹ disappeared completely. 18.45 g of an odorless pale yellow oil having a viscosity at 25 ° C. of 0.3 Pa · s was obtained.
FT-IR: 3367 (N-H), 2969, 2926, 2854, 1640 (C = N), 1449, 1372, 1342, 1297, 1255, 1100, 1014, 925, 889, 861, 715.

Catalyst K-4: 1,1 ′-(α, ω-polyoxypropylene) bis (2,3-dicyclohexylguanidine) having a molecular weight of about 2,400 g / mol
In a round bottom flask, polyoxypropylenediamine having an average molecular weight of about 2,000 g / mol (Jeffamine (registered trademark) D-2000 manufactured by Huntsman, amine content: about 1.0 meq / g), 24.06 g, N, N ′ -Dicyclohexylcarbodiimide 4.15g was mixed and the mixture was heated and stirred at 120 degreeC. The reaction mixture was examined by FT-IR spectroscopy at regular intervals. After 72 hours, the carbodiimide absorption band of about 2120 cm ⁻¹ disappeared completely. 28.21 g of an odorless pale yellow oil having a viscosity at 25 ° C. of 2.4 Pa · s was obtained.
FT-IR: 3367 (N-H), 2969, 2926, 2856, 1641 (C = N), 1449, 1372, 1343, 1296, 1256, 1097, 1013, 925, 866, 833, 715.

Catalyst K-5: 1,1 ′-(α, ω-polyoxypropylene) bis (2,3-diisopropylguanidine) having a molecular weight of about 690 g / mol
In a round bottom flask, 5.57 g of polyoxypropylenediamine (Jeffamine (registered trademark) D-400 manufactured by Huntsman, amine content of about 4.4 meq / g) having an average molecular weight of about 430 g / mol, and N, N′-diisopropyl 2.95 g of carbodiimide was mixed, and the mixture was heated and stirred at 120 ° C. The reaction mixture was examined by FT-IR spectroscopy at regular intervals. After 18 hours, the carbodiimide absorption band at about 2120 cm ⁻¹ disappeared completely. Thereafter, volatile components were removed from the reaction mixture under reduced pressure. 8.50 g of an odorless pale yellow oil having a viscosity at 25 ° C. of 0.4 Pa · s was obtained.
FT-IR: 3365 (N-H), 2955, 2929, 2967, 1640 (C = N), 1452, 1372, 1338, 1295, 1099, 1018, 923, 859, 845, 713.

Catalyst K-6: N, N ″-(α, ω-polyoxypropylene) bis (N′-hexylacetimidoamide) having a molecular weight of about 480 g / mol
In a test tube, polyoxypropylenediamine having an average molecular weight of about 230 g / mol (Jeffamine (registered trademark) D-230 manufactured by Huntsman, amine content of about 8.4 meq / g) 9.63 g, n-hexylamine 8.11 g, Then, 10.21 g of trimethyl orthoacetate and 0.33 g of lanthanum triflate were mixed and heated and stirred at 160 ° C. for 40 minutes at a maximum pressure of 150 Pa in a microwave heating apparatus. The reaction mixture was then transferred to a round bottom flask and volatile components were removed under reduced pressure. An odorless yellow oily substance 20.24g was obtained.
FT-IR: 3369, 2958, 2926, 2856, 1684, 1644, 1524, 1454, 1373, 1259, 1101, 1031, 926, 725.

Production of silane group-containing polymer:
Polymer STP-1:
Under anhydrous conditions, polyol Acclaim (R) 12200 (low unsaturation polyoxypropylene diol, manufactured by Bayer; OH number 11.0 mg KOH / g) 1000 g, isophorone diisocyanate (IPDI; Vestanat (R) IPDI, Evonik (43.6 g), diisodecyl phthalate (DIDP) 126.4 g, and tris (neodecanoic acid) bismuth (10 wt% DIDP) 0.1 g with constant stirring and titrated free isocyanate Leave at this temperature until the group content reaches a stable value of 0.63% by weight. Thereafter, N- (3-trimethoxysilylpropyl) -amino-succinic acid diethyl ester (addition of 3-aminopropyltrimethoxysilane and maleic acid diethyl ester; described in US Pat. No. 5,364,955) 63.0 g) and the mixture was stirred at 90 ° C. until no further free isocyanate was detected by FT-IR spectroscopy. The trimethoxysilane group-containing polyether having a silane equivalent of about 6880 g / Eq (calculated from the amount used) thus obtained was cooled to room temperature and stored under anhydrous conditions.

Polymer STP-2:
Under anhydrous conditions, polyol Acclaim (R) 12200 (low unsaturation polyoxypropylene diol, manufactured by Bayer; OH number 11.0 mg KOH / g) 1000 g, isophorone diisocyanate (IPDI; Vestanat (R) IPDI, Evonik (43.6 g), diisodecyl phthalate (DIDP) 126.4 g, and tris (neodecanoic acid) bismuth (10 wt% DIDP) 0.1 g with constant stirring and titrated free isocyanate Leave at this temperature until the group content reaches a stable value of 0.64% by weight. Thereafter, 70.6 g of N- (3-triethoxysilylpropyl) -amino-succinic acid diethyl ester (addition product of 3-aminopropyltriethoxysilane and maleic acid diethyl ester) was mixed, and the mixture was heated at 90 ° C. Stir until no more free isocyanate is detected by FT-IR spectroscopy. The triethoxysilane group-containing polyether having a silane equivalent of about 6920 g / Eq (calculated from the amount used) thus obtained was cooled to room temperature and stored under anhydrous conditions.

Commercial catalysts used and their abbreviations:
DBU 1,8-diazabicyclo [5.4.0] undec-7-ene TMG 1,1,3,3-tetramethylguanidine IBAY Tyzor® IBAY, bis (ethylacetoacetato) diisobutoxy-titanium (IV ), MTHP 2-methyl-1,4,5,6-tetrahydropyrimidine TMTHP 2,5,5-trimethyl-1,4,5,6-tetrahydropyrimidine DBTDL dibutyltin dilaurate (IV) manufactured by Dorf Ketal

Silane crosslinkable composition:
Compositions Z1 to Z25 are examples of the present invention, and compositions V1 to V26 are comparative examples.

Compositions Z1-Z2b and comparative V1-V5:
A composition consisting of 96.5 g of polymer STP-1, 0.5 g of vinyltrimethoxysilane and 3.0 g of 3-aminopropyltrimethoxysilane was mixed with the various catalysts described in Table 1 and stored. Before and after, the viscosity and film formation time (HBZ) of the mixture were tested in a standard atmosphere. The film formation time then serves as a measure of the catalytic activity for the crosslinking reaction of the silane groups, i.e. a measure of the crosslinking rate; the change in viscosity and film formation time after storage is a measure of storage stability. In addition, after 24 hours in a standard atmosphere, the applied mixture is subjected to whether the surface has been dried as desired or a sticky film has formed (this is poorly compatible with the cured plastic). ) And / or whether the surface is sticky (this is a sign of incomplete cure). In addition, a 2 mm thick film was formed from the mixture and cured for 7 days in a standard atmosphere and tested for mechanical properties. The results are shown in Tables 1 and 2. “Zus.” Represents “composition”.

Compositions Z3-Z11 and comparative V6-V11:
A composition consisting of 95.9 g of polymer STP-2, 0.4 g of vinyltriethoxysilane and 3.7 g of 3-aminopropyltriethoxysilane was mixed with the various catalysts in the amounts described according to Table 3, The mixture was tested for viscosity, film formation time (HBZ), surface properties and mechanical properties as described for composition Z1. The results are shown in Table 3 and Table 4. “Zus.” Represents “composition”.

Compositions Z12-Z14 and comparative V12-V13:
In a planetary mixer, 36.2 g of polymer STP-2, 60.2 g of crushed chalk (Omycarb (registered trademark) 5GU, manufactured by Omya), 1.2 g of thixotropic paste (the production will be described later), vinyl 1.2 g of triethoxysilane, 1.2 g of 3-aminopropyltriethoxysilane and various amounts of various catalysts according to Table 5 were mixed and the viscosity of the mixture, film formation time as described for composition Z1. (HBZ), surface properties and mechanical properties were tested. The results are shown in Table 5. “Zus.” Represents “composition”.

  The thixotropy paste is charged in a vacuum mixer with 300 g of diisodecyl phthalate (Palatinol (registered trademark) Z, manufactured by BASF) and 48 g of 4,4′-methylenediphenyl diisocyanate (Desmodur (registered trademark) 44 MCL, manufactured by Bayer), After gently heating, 27 g of n-butylamine was slowly added dropwise with vigorous stirring. The resulting paste was further stirred for 1 hour while cooling under reduced pressure.

Compositions Z15-Z16 and comparative V14-V15:
A composition consisting of 98 g of silane group-containing polyether MS Polymer ™ S203H (manufactured by Kaneka) and 2 g of 3-aminopropyltrimethoxysilane was mixed with various catalysts in the amounts indicated according to Table 6 and as described In addition, the film formation time (HBZ) of the mixture and the surface properties after 7 days were tested in a standard atmosphere. The results are shown in Table 6. “Zus.” Represents “composition”.

Compositions Z17-Z18 and comparative V16-V18:
A composition comprising 96.5 g of a silane group-containing polyether TEGOPAC® Bond 150 (manufactured by Evonik), 0.5 g of vinyltriethoxysilane, and 3.0 g of 3-aminopropyltriethoxysilane is described according to Table 7. Were mixed with various amounts of catalyst and the film formation time (HBZ) and surface properties after 7 days were tested in a standard atmosphere as described. The results are shown in Table 7. “Zus.” Represents “composition”.

Composition Z19 and comparative V20-V22
In a round bottom flask, 71.1 g of OH-terminated linear polydimethylsiloxane (Wacker® Silicone Rubber Polymer FD50, manufactured by Wacker) having a viscosity of about 50,000 mPas at 23 ° C. was added to vinyl-tris (methylethylketoximo). ) Mix with 2.6g of silane and stir for 15 minutes under reduced pressure. To the polydimethylsiloxane having vinyl-bis (methylethylketoximo) silyl end groups thus obtained, 26.3 g of trimethylsilyl-terminated polydimethylsiloxane (Wacker (registered trademark) AK100 Siliconoel, manufactured by Wacker) was added and stirred. did. This mixture was mixed with various catalysts according to the following Table 8 and tested for viscosity, film formation time (HBZ), surface properties and mechanical properties as described for composition Z1. The results are shown in Table 8 and Table 9. “Zus.” Represents “composition”.

Compositions Z20-Z21 and comparative V23-V24
In a plastic beaker, 99 parts by weight (GT) of OH-terminated linear polydimethylsiloxane (Wacker (registered trademark) Silicone Rubber Polymer FD50, manufactured by Wacker) having a viscosity of about 50,000 mPas at 23 ° C. and Wacker (registered trademark) 20.2 g of a first component consisting of 1 GT with E2 Siliconoel-Emulsion (medium viscosity OH-terminated linear polydimethylsiloxane emulsified in water with a nonionic emulsifier, manufactured by Wacker; solid content 37-40%), Intimately mixed with 0.80 g of vinyltrimethoxysilane and a second component of the type and amount of catalyst listed in Table 10, and as described for composition Z1, film formation time (HBZ) and surface properties of the mixture Was tested. In addition, the Shore A hardness of the applied mixture after 7 days in a standard atmosphere was tested. The results are shown in Table 10. “Zus.” Represents “composition”.

Composition Z22 (in situ production of the catalyst):
A composition comprising 30.0 g of polymer STP-1, 0.15 g of vinyltrimethoxysilane, and 1.2 g of 3-glycidoxypropyltrimethoxysilane was obtained under an anhydrous condition with an average molecular weight of about 430 g / mol. 0.8 g of polyoxypropylenediamine (Jeffamine® D-400 from Huntsman, amine content about 4.4 meq / g) and 0.4 g of N, N′-diisopropylcarbodiimide are mixed, The coated aluminum tube was filled and heated to 80 ° C. in an oven. According to the time intervals listed in Table 11, the film formation time (HBZ) in the standard atmosphere of the mixture and the conversion of carbodiimide (first due to a decrease in the strength of the carbodiimide absorption band at about 2120 cm ⁻¹ in FT-IR) Strength = 0% conversion, no more absorption band detectable = 100% conversion). The results are shown in Table 11.

Composition Z23 (in situ production of the catalyst):
The in situ preparation of the catalyst from composition Z22 was repeated except that 3-glycidoxypropyltrimethoxysilane was omitted. The results are shown in Table 12.

Compositions Z24-Z25 and comparative V25 and V26:
Silane group-containing polyether, GENIOSIL® STP-E15 (manufactured by Wacker) or Desmosal® S XP2821 (manufactured by Bayer) 96.0 g, vinyltrimethoxysilane 0.35 g, 3-aminopropyltrimethoxy A composition consisting of 3.72 g of silane was mixed with the indicated amounts of various catalysts according to Table 13 and the mixture was tested as described for composition Z1. The results are shown in Table 13. “Zus.” Represents “composition”.

Claims (13)

Formula (I)

{Where
n represents 1 or 2 or 3;
A represents a polyoxyalkylene group or a group of a polyoxyalkylated compound, optionally having one or two terminal primary or secondary amino groups or hydroxyl groups;
Z is the formula

Or

(Where
R ¹ represents hydrogen,
R ⁰ is represented hydrogen or an alkyl or cycloalkyl group or aralkyl group having 1 to 8 carbon atoms,
R ³ represents ^-NR 4 ^{R 5,}
R ² and R ⁵ represent independently of one another are alkyl groups having 1 to 18 carbon atoms containing their respective cases by a heteroatom, a cycloalkyl group or an aralkyl group,
R ⁴ represents a hydrogen group)}
A crosslinking catalyst in the curable composition of
A catalyst of formula (I) that does not contain a nitrogen atom directly attached to an aromatic ring or part of an aromatic heterocyclic ring system. The catalyst according to claim 1 , wherein the average molecular weight of A is in the range of 180 to 5,000 g / mol.   A is a polyoxypropylene group optionally having another oxyalkylene unit moiety, or optionally a poly (oxytetramethylene) group having a 1,2-oxypropylene unit moiety, or 1,2-propylene oxide as an alcohol. And represents a 1 to 3 valent group of a polyoxyalkylated compound obtained by polyaddition to a starting material molecule selected from the group consisting of fatty alcohol, alkylphenol, diol, and triol. Or the catalyst according to 2. Each Ethyl independently R ² and ^{R 5} each other, isopropyl, tert- butyl, 3- (dimethylamino) propyl or characterized to represent cyclohexyl,, according to any one of claims 1 to 3 catalyst. R ³ represents ^-NR 4 ^{R 5,} a process for preparing a catalyst according to any one of claims 1-4, at least one polyetheramine of the formula A- ^(NHR _{1) n,} Reacting with at least one carbodiimide of the formula R ⁵ —N═C═N—R ² . The polyetheramine optionally comprises a polyoxypropylene diamine having a portion of another oxyalkylene unit, or optionally a poly (tetramethylene ether) diamine having a 1,2-oxypropylene unit, or 1,2-propylene oxide. Polyether monoamines or polyether diamines or polyether triamines mainly comprising 1,2-oxypropylene units obtained by polyaddition to starting material molecules selected from the group consisting of alcohols, fatty alcohols, alkylphenols, diols, and triols. 6. The method according to claim 5 , characterized in that it is. Use of the catalyst according to any one of claims 1 to 4 as a crosslinking catalyst in a curable composition. Use according to claim 7 , characterized in that the curable composition is an adhesive, a sealing material or a coating material. The curable composition containing the at least 1 sort (s) of catalyst as described in any one of Claims 1-4 . The curable composition according to claim 9 , comprising at least one silane group-containing polymer. The silane group containing polymer, characterized in that it is a mixed silane group-containing polyolefin or a silane group-containing polyester or a silane group-containing poly (meth) acrylate or silane group-containing polyethers or their polymers, according to claim 1 0 The curable composition according to 1. Further characterized in that it contains at least one organotitanate, curable composition according to any one of claims 9-1 1. Cured composition obtained after curing a curable composition according to any one of claims 9-1 2.